Substituted fluorophosphazenes

ABSTRACT

New and valuable substituted fluorophosphazenes, pesticides containing these compounds, and a process for controlling pests with these compounds.

This application discloses and claims subject matter described in GermanPat. Application No. P 23 34 917.9, filed July 10, 1973, which isincorporated herein by reference.

The present invention relates to new and valuable substitutedfluorophosphazenes, a process for controlling pests with thesecompounds, and pesticides containing these compounds as activeingredients.

We have found that substituted fluorophosphazenes of the formula

    N.sub.3 P.sub.3 F.sub.n Z.sub.6 .sub.-n,

where Z denotes OR, OT, SR, SY, NHNHR, NHCSR, ##EQU1## NHCOXR orNHCONR₂, R, R' and R" denoting alkyl or aryl, X denoting oxygen orsulfur, T denoting alkyl and Y denoting alkyl of more than 2 carbonatoms, and n denotes one of the integers 2, 3, 4 and 5, n being 4 or 5when Z is NHNHR, nbeing 2, 3 or 4 when Z is OR, n being 2, 3 or 4 when Zis SR, and n otherwise being 5, are excellently suited for controllingpests.

The active ingredients are generally prepared from cyclic phosphorusnitride fluorides. To obtain compounds of the formulas N₃ P₃ F_(n) (OR)₆_(-n) or N₃ P₃ F_(n) (SR)₆ _(-n), the esters and thioesters of thefluorophosphazenes, a solution of the phosphorus nitride fluoride isgenerally reacted in a solvent, e.g., ether, THF (tetrahydrofuran),benzene, toluene, chlorobenzene and alcohol, with the calculated amountof alcoholate or mercaptide, e.g., in the form of the sodium salt. Thereaction is generally carried out at temperatures of from -20° to+100°C, preferably from 0° to 90° C. The fluorophosphazenes prepared inthis manner are usually colorless liquid compounds which can generallybe purified by distillation.

The reaction of NaSCH₃ with N₃ P₃ F₆ to give N₃ P₃ F₄ (SCH₃)₂ proceedsin accordance with the equation

    N.sub.3 P.sub.3 F.sub.6 + 2 NaSCH.sub.3 → N.sub.3 P.sub.3 F.sub.4 (SCH.sub.3).sub.2 + 2 NaF.

the fluorophosphazene hydrazine derivatives N₃ P₃ F_(n) (NHNHR)₆ _(-n)are obtained by reacting the fluorophosphazene in a solvent, e.g.,ether, THF, benzene and chlorobenzene, with the calculated amount of thehydrazine.

The reaction is generally carried out at temperatures of from -40° to+140° C, preferably 0° to 100° C, in the presence or absence ofacid-binding agents. Particularly preferred as such are tertiary aminesor heterocyclic amines, e.g., pyridine. However, a 100% excess of theprimary or secondary amine may also be used as acid acceptor, e.g., inaccordance with the equation

    N.sub.3 P.sub.3 F.sub.6 + 2 H.sub.2 NNHCH.sub.3 → N.sub.3 P.sub.3 F.sub.5 NHNHCH.sub.3 + H.sub.2 NNHCH.sub.3. HF.

the fluorophosphazene acid amide derivatives are obtained as follows. Iffluorophosphazenimine chloride, ##EQU2## is reacted with athiocarboxamide, the corresponding fluorophosphazene thioacid amidederivative is obtained in almost quantitative yield. With thioacetamidethe reaction proceeds in accordance with the following equation:##EQU3##

The reaction may be carried out in a solvent, e.g., ether, THF andbenzene, at atmospheric or superatmospheric pressure and at temperaturesof from 10° to 100°C.

The compounds ##EQU4## are obtained starting from the from theappropriate fluorophosphazenimine chloride ##EQU5## by reaction with asalt (preferably sodium) of a thiophosphoric acid ester, e.g., NaSP(O)(OR)₂.

Solvents, e.g., ether, THF, benzene, toluene and chloroform, aregenerally used in the reaction.

The reaction is best carried out at a temperature of from -10° to +110°C. ##EQU6##

If the phosphazenimine chloride is reacted with a phosphite as in anArbusov reaction, it is not the expected imine compound which is formedwith the elimination of methyl chloride but theN-fluorophosphazeno-α-dimethoxyphosphonylenamine.

With trimethyl phosphite the reaction proceeds according to thefollowing equation: ##EQU7##

The reaction may be carried out in the presence or absence of a solvent,e.g., ether, THF, chlorinated hydrocarbons (CHCl₃, CH₂ Cl) and aromatichydrocarbons (benzene, toluene). The temperature is generally from 10°to 150° C.

Previous attempts to prepare fluorophosphazene isocyanate, N₃ P₃ F₅ NCO,by reaction of N₃ P₃ F₅ NSO with oxalyl chloride only resulted in yieldsof 8%, Z. Naturforsch. (H.W. Roesky, E. Janssen), 26b, 679 et seq.,1971.

We have now found that N₃ P₃ F₅ NCO may be prepared in surprisingly highyields by converting the N-sulfynylamine group NSO on the N₃ P₃ F₅radical to the isocyanate group with COCl₂. It is preferred first toplace N₃ P₃ F₅ NSO in a solvent, generally one boiling at above 110° C,e.g., chlorobenzene and tetrachloroethane, and then to pass in phosgeneat a temperature of from 20° to 100° C, preferably 70° to 100° C. Anexcess of phosgene is not detrimental.

The reaction may be accelerated by adding catalytic amounts of pyridine,preferably from 0.01 to 1 ml per 100 g of N₃ P₃ F₅ NSO.

For working up, first the SOCl₂ and subsequently the N₃ P₃ F₅ NCO aredistilled off.

    N.sub.3 P.sub.3 F.sub.5 NSO + COCl.sub.2 → N.sub.3 P.sub.3 F.sub.5 NCO + SOCl.sub.2

The fluorophosphazene isocyanate which may be readily prepared in largeamounts in this way is very reactive and may be used as an intermediatefor a variety of products.

Aliphatic and aromatic amines give the corresponding urea derivatives.What is remarkable is that the ring itself is not attacked by an excessof amine, e.g.:

    N.sub.3 P.sub.3 F.sub.5 NCO + NHR.sub.2 → N.sub.3 P.sub.3 F.sub.5 NHCONR.sub.2,

r denoting alkyl or aryl.

Phosphates containing the carbamate or thiocarbamate radical assubstituent are formed with alcohols and thioalcohols:

    N.sub.3 P.sub.3 F.sub.5 NCO + HOC.sub.2 H.sub.5 → N.sub.3 P.sub.3 F.sub.5 NHCOOC.sub.2 H.sub.5.

some of the derivatives of isocyanate fluorophosphazenes are distillableliquids, others crystallizable substances, and they are stable tohydrolysis. They are preferably prepared in solvents, e.g., ether, THF,benzene, toluene, and chloroform, and at temperatures of from -10° to+120° C.

EXAMPLE 1 Preparation of N₃ P₃ F₅ (SCH₃)₂

At -20°C and while stirring, a slurry of 56 parts (by weight) of NaSCH₃in 300 parts of ether is added to a solution of 100 parts of N₃ P₃ F₆ in400 parts of ether. After 30 minutes the reaction is brought to thereflux temperature and boiled at this temperature for 4 hours.Subsequently, the NaF is removed by filtration. The compound is purifiedby fractional distillation.

Yield: 66 parts = 54% of theory, with reference to N₃ P₃ F₆ ; b.p. (3mm): 49° to 53° C.

EXAMPLE 2 Preparation of N₃ P₃ F₂ (OCH₃)₄

In a manner similar to that described in Example 1 a slurry of 86 partsof NaOCH₃ in 400 parts of ether is added, at -60° C and while stirring,to 100 parts of N₃ P₃ F₆ in 200 parts of ether. After the temperature ofthe reaction mixture has risen to +20° C, it is boiled under reflux for6 hours. Subsequently, the NaF is filtered off. The compound is purifiedby fractional distillation. Yield: 59 parts = 49% of theory; b.p. (0.1mm): 52° to 54° C,

The following compounds may be prepared in the same manner as in Example1:

                    b.p. (mm)                                                                              °C                                            ______________________________________                                        N.sub.3 P.sub.3 F.sub.3 (SCH.sub.3).sub.3                                                       0.1        80                                               N.sub.3 P.sub.3 F.sub.4 (OCH.sub.3).sub.2                                                       67         93                                               N.sub.3 P.sub.3 F.sub.3 (OCH.sub.3).sub.3                                                       0.01       45 to 47                                         N.sub.3 P.sub.3 F.sub.4 (OC.sub.2 H.sub.5).sub.2                                                0.01       33 to 35                                         N.sub.3 P.sub.3 F.sub.3 (OC.sub.2 H.sub.5).sub.3                                                0.01       59 to 62                                         N.sub.3 P.sub.3 F.sub.2 (OC.sub.2 H.sub.5).sub.4                                                0.01       137                                              N.sub.3 P.sub.3 F.sub.4 (OCH.sub.2 CH.sub.2 CH.sub.3).sub.2                                     0.01       43                                               N.sub.3 P.sub.3 F.sub.2 (OCH.sub.2 CH.sub.2 CH.sub.3).sub.4                                     0.01       90 to 95                                         ______________________________________                                    

EXAMPLE 3 Preparation of N₃ P₃ F₅ NHNHCH₃

At -10° C. 18.4 parts of H₂ NNHCH₃ in 50 parts of ether is slowlydripped into a solution of 50 parts of N₃ P₃ F₆ in 200 parts of ether.The mixture is heated to 25° C and stirred at this temperature for 2hours. Subsequently, the HF.H₂ NNHCH₃ is filtered off, the filtrate isconcentrated and the residue fractionally distilled at 6 mm. Thefraction distilling between 63° and 72° C (mainly N₃ P₃ F₅ NHNHCH₃) isrecrystallized from hexane.

Yield: 46.4 parts = 84% of theory, with reference to N₃ P₃ F₆ ; m.p.:80° C.

The following compound is prepared in the same manner: N₃ P₃ F₅NHN(CH₃)₂ b.p. (35 mm): 83° to 85° C

EXAMPLE 4 Preparation of ##EQU8##

At room temperature, 50 parts of ##EQU9## is dripped into 12.3 parts of##EQU10## in 150 parts of ether, and the mixture stirred for 4 hours atthis temperature. The mixture is subsequently concentrated and theresidue recrystallized from heptane.

Yield: 35.1 parts = 71% of theory, with reference to ##EQU11## m.p.: 89°C.

EXAMPLE 5 Preparation of ##EQU12##

At room temperature, 50 parts of ##EQU13## is dripped into 36 parts ofNH₄ SP(O)(OC₂ H₅)₂ in 100 parts of benzene. A precipitate formsimmediately. The mixture is stirred for 4 hours at 40° C andsubsequently filtered. The filtrate is concentrated, the residue istaken up in hexane and filtered through activated carbon, and the hexaneis filtered at 50° C in a water-jet vacuum. There remains 43 parts (56%of theory) of a pale yellow, undistillable oil which according toultimate analysis and infrared spectra has the composition ##EQU14##

EXAMPLE 6 Preparation of ##EQU15##

30 parts of P(OCH₃)₃ in 50 parts of benzene is added to 50 parts of##EQU16## in 300 parts of benzene. The mixture is subsequently boiledunder reflux for 90 minutes. The benzene and excess phosphite aredistilled off and the residue is fractionally distilled at 0.01 mm.

Yield: 57 parts = 92% of theory; b.p. (0.01 mm): 100° C.

The following compounds are prepared in the same manner as in Example 6:

                   b.p. (mm)                                                                            °C m.p. °C                                ______________________________________                                        ∥                                                                    P=(OC.sub.2 H.sub.5).sub.2                                                    N.sub.3 P.sub.3 F 5NH--C∠                                                                0.01     105       58 to 59                                  CH.sub.2                                                                      O                                                                             ∥                                                                    P=(OCH.sub.3).sub.2                                                           N.sub.3 P.sub.3 F.sub.5 NH--C∠                                                           0.01     113 to 115                                          CH--CH.sub.3                                                                  ______________________________________                                    

EXAMPLE 7 Preparation of N₃ P₃ F₅ NCO

0.25 part of pyridine is added to 100 parts of N₃ P₃ F₅ NSO in 300 partsof chlorobenzene. At 95° C, 40 parts of phosgene is passed in over aperiod of 2 hours. The SOCl₂ which has formed is distilled off, andsubsequently N₃ P₃ F₅ NCO.

Yield: 65 parts = 85% of theory; b.p. (760 mm): 100° C.

EXAMPLE 8 Preparation of N₃ P₃ F₅ NHCOOCH₃

8.1 parts of CH₃ OH is added to 50 parts of N₃ P₃ F₅ NCO in 150 parts ofether, and the mixture boiled under reflux for 2 hours. The solvent isthen distilled off and the residue recrystallized from hexane.

47 parts (87% of theory) of white crystals of the desired compound isobtained; m.p.: 72° to 73° C.

The following compounds were obtained in the same manner as in Example8:

                 b.p. (mm)                                                                              °C                                                                             m.p. °C                                  ______________________________________                                        N.sub.3 P.sub.3 F.sub.5 NHCOOC.sub.2 H.sub.5                                                 0.1        41      --                                          N.sub.3 P.sub.3 F.sub.5 NHCOSC.sub.2 H.sub.5                                                 0.01       99      --                                          N.sub.3 P.sub.3 F.sub.5 NHCON(C.sub.2 H.sub.5).sub.2                                         --         --      115                                         ______________________________________                                    

Application may be effected for instance in the form of directlysprayable solutions, powders, suspensions, dispersions, emulsions, oildispersions, pastes, dusts or granules. The forms of application dependentirely on the purpose for which the agents are being used; in any casethey should ensure a fine distribution of the active ingredient.

For the preparation of solutions, emulsions, pastes and oil dispersionsto be sprayed direct, mineral oil fractions of medium to high boilingpoint, such as kerosene or diesel oil, further coal-tar oils and oils ofvegetable or mineral origin, aliphatic, cyclic and aromatic hydrocarbonssuch as benzene, toluene, xylene, paraffin, tetrahydronaphthalene,alkylated naphthalenes, methanol, ethanol, propanol, butanol,chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone,chlorobenzene, isophorone, etc., and strongly polar solvents such asdimethylformamide and dimethyl sulfoxide are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes,oil dispersions or wettable powders by adding water. To prepareemulsions, pastes and oil dispersions the ingredients as such ordissolved in an oil or solvent may be homogenized in water by means ofwetting or dispersing agents, adherents or emulsifiers. Concentrateswhich are suitable for dilution with water may be prepared from activeingredient, wetting agent, adherent, emulsifying or dispersing agent andpossibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of ligninsulfonic acid, naphthalenesulfonic acids,phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkylsulfonates, alkali metal and alkaline earth metal salts ofdibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcoholsulfates, alkali metal and alkaline earth metal salts of fatty acids,salts of sulfated hexadecanols, heptadecanols, and octadecanols, saltsof sulfated fatty alcohol glycol ether, condensation products ofsulfonated naphthalene and naphthalene derivatives with formaldehyde,condensation products of naphthalene or naphthalenesulfonic acids withphenol and formaldehyde, polyoxyethylene octylphenol ethers ethoxylatedisooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcoholethylene oxide condensates, ethoxylated castor oil, polyoxyethylenealkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycolether acetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silica gel, silicic acid,silicates, talc, kaolin, Attaclay, limestone, lime chalk, bole, loess,clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground plastics, fertilizers such as ammonium sulfate,ammonium phosphate, ammonium nitrate, and ureas, and vegetable productssuch as grain flours, bark meal, wood meal, and nutshell meal,cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably from 0.5 to 90,% by weight of active ingredient.

There may be added to the compositions or individual active ingredients(if desired, immediately before use) oils of various types, herbicides,fungicides, nematocides, insecticides, bactericides and trace elements.

These agents may be added to the agents of the invention in a ratio byweight of from 1:10 to 10:1.

Examples of pests are termites, e.g., Reticulitermes sp., Macrotermessp., Microtermes sp., and Kalotermes sp.; ligniperdous beatles, e.g.,Hylotrupes bajulus (house longhorn), Anobium punctatum, and Lyctus sp.;flies, e.g., Musca domestica, Fannia canicularis, Muscina stabulans, andStomoxys calcitrans; mosquitoes, e.g., Aedes sp., Culex sp., Anophelessp. Phlebotomus sp., and Simulium sp.; cockroaches, e.g., Blatta sp.,Blatella sp., and Periplaneta; butterflies, e.g., Spodoptera sp.,Heliothis sp., Plutella sp., Earias sp., and Ephestia sp.; andfresh-water snails, e.g., Planorbis sp., and Australorbis sp.

The following active ingredients were used in the experiments: ##EQU17##

Comparative agents

I. Decachlorotetracyclodecanone (U.S. Pat. No. 2,616,825) ##EQU18##

EXAMPLE 9 Contact action on oriental cockroach (Blatta orientalis)

1 liter beakers are wetted with acetonic solutions of the activeingredients. After evaporation of the solvent, cockroaches are placed inthe beakers. The action is determined after 48 hours.

    ______________________________________                                                      Amount of active                                                Active ingredient                                                                           ingredient     Mortality                                        ______________________________________                                        I               10.0    mg       100%                                                         5.0     mg       20%                                          II              5.0     mg       20%                                          2               2.5     mg       100%                                         3               0.2     mg       100%                                                         0.1     mg       80%                                          4               0.5     mg       100%                                                         0.25    mg       80%                                          5               0.25    mg       100%                                         ______________________________________                                    

EXAMPLE 10 Contact action on houseflies (Musca domestica)

Petri dishes 10 cm in diameter are uniformly wetted with acetonicsolutions of the active ingredients. After evaporation of the solvent,20 4-day-old houseflies are placed in each dish and the mortality rateis determined after 4 hours.

    ______________________________________                                                      Amount of active                                                Active ingredient                                                                           ingredient     Mortality                                        ______________________________________                                        I               2.0     mg       40%                                          II              2.0     mg       10%                                          2               0.2     mg       80%                                          3               0.02    mg       100%                                         4               0.2     mg       100%                                         5               0.2     mg       100%                                         ______________________________________                                    

EXAMPLE 11 Action on larvae of the yellow fever mosquito (Aedes aegypti)

Larvae of the yellow fever mosquito in the 3rd and 4th development stageare placed in 100 ml of water to which aqueous emulsions of the activeingredients are added. The mortality rate is determined after 24 hours.

    ______________________________________                                                      Amount of active                                                Active ingredient                                                                           ingredient     Mortality                                        ______________________________________                                        I               5.0     ppm      ineffective                                  1               0.5     ppm       95%                                         2               1.0     ppm      100%                                         3               2.0     ppm       90%                                         4               0.5     ppm      100%                                                         0.25    ppm       80%                                         6               1.0     ppm      100%                                         ______________________________________                                    

EXAMPLE 12 Contact action and effect of ingested food on caterpillars ofthe cabbage moth (Plutella maculipennis)

Young cabbage leaves are dipped for 5 seconds into aqueous emulsions ofthe active ingredients. After the layer has dried, caterpillars in the4th and 5th larval stages are placed on the leaves. The action isassessed after 48 hours.

    ______________________________________                                                      Amount of active                                                Active ingredient                                                                           ingredient     Mortality                                        ______________________________________                                        I             0.1%           90%                                                            0.05%          80%                                              1             0.05%          100%                                             2             0.01%          100%                                             3             0.005%         80%                                              4             0.005%         80%                                              6             0.02%          80%                                              ______________________________________                                    

EXAMPLE 13 Action on freshwater snails (Planorbis)

Aqueous emulsions of the active ingredients are added to 100 ml ofwater. Adult snails are used. The action is assessed after 48 hours.

    ______________________________________                                                        Amount of active                                              Active ingredient                                                                             ingredient   Mortality                                        ______________________________________                                        I               1.0     ppm      100%                                                         0.5     ppm      20%                                          1               0.1     ppm      100%                                                         0.05    ppm      80%                                          4               0.05    ppm      100%                                         6               0.05    ppm      80%                                          ______________________________________                                    

We claim:
 1. A substituted fluorophosphazene of the formula

    N.sub.3 P.sub.3 F.sub.n Z.sub.6 .sub.-n,

where Z denotes OR or SR, wherein R denotes lower alkyl and n denotesone of the integers 2, 3, or
 4. 2. A compound as claimed in claim 1wherein Z is OR.
 3. A compound as claimed in claim 2 wherein R is --CH₃.4. A compound as claimed in claim 2 wherein R is --CH₃ and n is
 4. 5. Acompound as claimed in claim 2 wherein R is --CH₃ and n is
 3. 6. Acompound as claimed in claim 2 wherein R is --C₂ H₅ and n is 2, 3 or 4.7. A compound as claimed in claim 2 wherein R is --CH₂ CH₂ CH₃ and n is2.
 8. A compound as claimed in claim 2 wherein R is --CH₂ CH₂ CH₃ and nis
 4. 9. A compound as claimed in claim 1 wherein Z is --SCH₃ and n is3.
 10. A compound of the formula ##EQU19##
 11. A compound of the formula##EQU20##